CN1328254C - Metal bis-triflimide compounds and methods for synthesis of metal bis-triflimide compounds - Google Patents

Metal bis-triflimide compounds and methods for synthesis of metal bis-triflimide compounds Download PDF

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CN1328254C
CN1328254C CNB028094212A CN02809421A CN1328254C CN 1328254 C CN1328254 C CN 1328254C CN B028094212 A CNB028094212 A CN B028094212A CN 02809421 A CN02809421 A CN 02809421A CN 1328254 C CN1328254 C CN 1328254C
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imines
fluoroform sulphonyl
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metal
ntf
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CN1507371A (en
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M·J·厄尔
B·J·麦考利
A·拉马尼
K·R·塞登
J·M·汤姆森
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Queens University of Belfast
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Abstract

A metal bis-triflimde compound having the formula: [Mx]n+[(N(SO2CF3)2)(nx-yz)](nx-yz)- [Ly]z- where M is a metal selected from the metals in groups 5 to 10, 12 and 14 to 16 and Cu, Au, Ca, Sr, Ba, Ra, Y, La, Ac, Hf, Rf, Ga, In, Tl, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, and the actinides; L is a negative or neutral ligand; n is 2, 3, 4, 5, 6, 7 or 8; x is greater than or equal to 1; y is 0, 1, 2, 3, 4, 5, 6, 7 or 8; and z is 0, 1, 2, 3 or 4.

Description

The synthetic method of metal two (fluoroform sulphonyl) group with imine moiety and metal two (fluoroform sulphonyl) group with imine moiety
The present invention relates to metal two (fluoroform sulphonyl) imines (bis-triflimide) compound and synthetic method thereof.
Existing known road sub-fraction metal two (fluoroform sulphonyl) group with imine moiety.WO99/40124 discloses two (fluoroform sulphonyl) imines titaniums and zirconium and has passed through AgN (SO 2CF 3) 2With R 1R 2MCl 2Reaction and the preparation method that carries out, wherein M is Ti or Zr; R 1Be indenyl, cyclopentadienyl or pentamethyl-cyclopentadienyl, R 2Be indenyl, cyclopentadienyl, pentamethyl-cyclopentadienyl, methyl, methoxyl group, hydroxyl, 2,4 independently, 6-trimethylammonium phenoxy group, trifluoro ethoxy, hexafluoro isopropoxy or chlorine.Two (fluoroform sulphonyl) imines aluminium and two (fluoroform sulphonyl) imines ytterbiums (yttberium) known (Synlett, in February, 1996,171 pages).Two (fluoroform sulphonyl) imines scandium also known (Synlett, in September, 1996,839 pages).Two (fluoroform sulphonyl) imines magnesium and lithium also known (1997,2645 pages of Tetrahedron Letters).
The catalyzer of chemical reaction is extremely important in chemistry.The compound of known some metal plays the effect of Lewis acid (electron pair acceptor(FPA)), and its reactant (and product) with reaction interacts, and causes speed of reaction to increase and/or the selectivity increase.The salt of the known metal (such as transition metal) that can exist with various oxidation state is catalyzed chemical reaction also.The example of these reactions has Friedel-Crafts reaction, oxidizing reaction, reduction reaction, Diels-Alder reaction, isomerization reaction, coupled reaction, addition reaction and elimination reaction.Catalyzer is divided into two classes: catalyzer and reactant and/or product same mutually homogeneous catalyst and catalyzer and reactant and/or product at out of phase heterogeneous catalyst.Homogeneous catalyst is characterised in that to have hyperergy and transformation efficiency but be difficult to and the isolating characteristic of reaction product.Heterogeneous catalyst is characterised in that to have less reactive and than low-conversion but can be more directly and the isolating characteristic of reaction product.Therefore need have hyperergy and high conversion and can be easily and the isolating raw catalyst of reaction product.
The invention provides a kind of metal two (fluoroform sulphonyl) group with imine moiety, it has following general formula:
[M x] n+[(N(SO 2CF 3) 2) (nx-yz)] (nx-yz)-[Ly] z-
M is the metal that is selected from periodic table of elements Pb, Ga, In, Pm, Sm, Gd, Tb, Ho, Er, Tm, Lu and actinide elements in the formula;
L is negativity or neutral ligand;
N is 2,3,4,5,6,7 or 8;
X is more than or equal to 1;
Y is 0,1,2,3,4,5,6,7 or 8;
Z is 0,1,2,3 or 4.
Described metal two (fluoroform sulphonyl) imines also refers to metal two (fluoroform sulphonyl) imines (bis-trifluoromethanesulfonimide).M can represent more than one metal ion.Described positively charged ion is preferably+2 ,+3 or+positively charged ion of 4 oxidation state, but also can be+1 ,+5 ,+6 ,+7 or+positively charged ion of 8 oxidation state.Preferred M is selected from Ga, In and Pb.More preferably M is selected from Pb (II), Ga (III), In (II) and In (III).The example of compound of the present invention has two (fluoroform sulphonyl) imines gallium, two (fluoroform sulphonyl) imines indium and two (fluoroform sulphonyl) imines lead.
L optional from oxygenatedchemicals (oxos) (as VO 2+), phosphine (as triphenyl phosphine), water, halogenide or ketone.Ligand can come from the reaction mixture of preparation catalyzer or use solvent, reagent or by product in the reaction mixture of ligand.
Do not prepare compound of the present invention in the past.Have been found that these compounds are effective especially catalyzer for common reaction by Louis acid catalysis.They are suitable for the chemical transformation of many Louis acid catalysis or mediation.They have the advantage that is better than Lewis acid such as aluminum chloride (III): they can not form strong complex compound with the reactant or the product of chemical transformation.They are particularly suitable for the acidylate or the alkylation of Friedel-Crafts reaction such as aromatic substance.They also can be used for the sulfonylation of aromatic substance.In the friedel-crafts acylation reaction, " catalyzer " normally a kind of stoichiometry reagent.But catalyst loading can reduce now; Be low to moderate 1% (mole) metal two (fluoroform sulphonyl) imines and can in the friedel-crafts acylation reaction, obtain quantitative yield.Compound of the present invention is with the finite concentration catalyzed chemical reaction, and described concentration is 0.0000001-1000% (mole), preferred 0.1-20% (mole), more preferably 0.5-5% (mole).This has reduced the catalyzer waste.Because many metals two (fluoroform sulphonyl) group with imine moiety have can be various the metal that exists of oxidation state, this makes their be fit to oxidation and reduction chemical transformation.Other can comprise isomerization reaction, coupled reaction with the chemical transformation that metal two (fluoroform sulphonyl) group with imine moiety obtains, take off coupling, condensation (comprising alcohol aldehyde and claisen condensation), polymerization, oligomeric, dimerization, addition, cancellation, addition/cancellation, hydration, dehydration, hydrogenation, dehydrogenation, halogenation, sulfonation and nitrated.
Metal two of the present invention (fluoroform sulphonyl) imines may dissolve in or part dissolves in or be insoluble to reactant or product.In this case, they can not only play solvent action but also play catalyst action.They may dissolve in, be insoluble to or part dissolves in molecular solvent or comprises in the solvent of supercritical solvent, perhaps solubilized or be suspended in ionic liquid (under temperature of reaction for liquid and under room temperature (promptly 20 ℃) or nearly room temperature (but also nonessential) fused melting salt usually).Under all these situations, described metal two (fluoroform sulphonyl) imines can work to influence the catalyzer or the reagent of chemical transformation.When compound of the present invention dissolved in or partly dissolve in reactant, described reaction can be carried out under solvent-free.
Therefore, the present invention also provides a kind of being used to carry out electrophilic substitution or isomery, the polymerization of aromatic ring or be rearranged into chemical compound or the method for molecule, and this method is by the metal two of following formula (fluoroform sulphonyl) group with imine moiety catalysis and solvation
[M x] n+[(N(SO 2CF 3) 2) (nx-yz)] (nx-yz)-[L y] z-
M is the metal that is selected from periodic table of elements 5-10 family, 12 families and 14-16 family and Cu, Au, Ca, Sr, Ba, Ra, Y, La, Ac, Hf, Rf, Pb, Ga, In, Tl, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and actinide elements in the formula;
L is negativity or neutral ligand;
N is 2,3,4,5,6,7 or 8;
X is more than or equal to 1;
Y is 0,1,2,3,4,5,6,7 or 8;
Z is 0,1,2,3 or 4.
Described metal two (fluoroform sulphonyl) imines also refers to metal two (fluoroform sulphonyl) imines.M can represent more than one metal ion.M is preferably selected from 7,8,9,10,12 and 14 families of the periodic table of elements.8 families are meant the family that comprises Fe, Ru, Os, Hs; 9 families are meant the family that comprises Co, Rh, Ir, Mt etc.Described positively charged ion is preferably+2 ,+3 or+positively charged ion of 4 oxidation state, but also can be+1 ,+5 ,+6 ,+7 or+positively charged ion of 8 oxidation state.Preferred M is selected from Mn, Fe, Co, Ni, In, Zn and Pb.More preferably M is selected from Mn (II), Fe (III), Co (II), Ni (II), In (III), Pb (II), In (II) and Ga (III).The example of compound of the present invention has two (fluoroform sulphonyl) imines calcium, two (fluoroform sulphonyl) imines strontium, two (fluoroform sulphonyl) imines barium, two (fluoroform sulphonyl) imines gallium, two (fluoroform sulphonyl) imines indium, two (fluoroform sulphonyl) imines scandium, two (fluoroform sulphonyl) imines yttrium, two (fluoroform sulphonyl) imines lanthanum, two (fluoroform sulphonyl) imines cerium, two (fluoroform sulphonyl) imines chromium, two (fluoroform sulphonyl) imines manganese, two (fluoroform sulphonyl) imines iron, two (fluoroform sulphonyl) imines cobalt, two (fluoroform sulphonyl) imines nickel, two (fluoroform sulphonyl) imines copper, two (fluoroform sulphonyl) imines zinc, two (fluoroform sulphonyl) imines cadmium, two (fluoroform sulphonyl) imines tin, plumbous and two (fluoroform sulphonyl) the imines bismuth of two (fluoroform sulphonyl) imines.
L optional from oxygenatedchemicals (oxos) (as VO 2+), phosphine (as triphenyl phosphine), water, halogenide or ketone.Ligand can come from the reaction mixture of preparation catalyzer or use solvent, reagent or by product in the reaction mixture of ligand.
Perhaps, described compound solubilized or be suspended in the ionic liquid, and reaction can be carried out in the optional medium that is provided by conventional solvent such as methylene dichloride.So, thereby compound of the present invention provides can use the advantage of having avoided needing to use explosive solvent such as Nitromethane 99Min. and noxious solvent such as methylene dichloride under condition of no solvent or in the presence of ionic liquid.In addition, when using metal two of the present invention (fluoroform sulphonyl) when imines reacts at condition of no solvent or in the presence of ionic liquid, they recycle easily.
Particularly, studied metal two (fluoroform sulphonyl) imines Zn (N (SO 2CF 3) 2) 2The X-ray crystal structure and think that it has caused its excellent catalytic property just.The structure of metal two (fluoroform sulphonyl) group with imine moiety is considered to be similar to the structure of two (fluoroform sulphonyl) imines zinc, and their X-ray crystal structure is shown in Fig. 5 to 7.
As seeing from the structure of two (fluoroform sulphonyl) imines zinc (II), it is by two two (fluoroform sulphonyl) imido grpup formations by Sauerstoffatom (being not nitrogen-atoms) with the metal-complexing of two (fluoroform sulphonyl) imines ion.Two remaining on atoms metal octahedral coordination points are by adjacent Zn (NTf 2) 2Sauerstoffatom insert.Because some metals two (fluoroform sulphonyl) group with imine moiety is volatile compound, believe from the coordination of adjacent metal two (fluoroform sulphonyl) imido grpup may be quite a little less than.
Compound of the present invention is a volatile compound, so it is applicable to metal or the metallic compound vacuum deposition processes on solid surface.This can obtain by metallic compound being sublimate into the non-metallic part of also removing compound on the solid surface when needed.Compound of the present invention is in vacuum or under normal pressure, is volatile being lower than 1000 ℃, more especially being lower than under 400 ℃ the temperature particularly.Table 1 has provided the boiling point/sublimation point (dec. represents to decompose) of metal two (fluoroform sulphonyl) group with imine moiety.
Table 1
Metal two (fluoroform sulphonyl) imines Boiling point under 1mmHg/℃
Mg(NTf 2) 2 300
Ca(NTf 2) 2 400 (decomposition)
Ni(NTf 2) 2 280
Co(NTf 2) 2 300 (decomposition)
Fe(NTf 2) 2 280
Ni(NTf 2) 2 280
Cu(NTf 2) 2 180 (decomposition)
Zn(NTF 2) 2 260
Cd(NTF 2) 2 350 (decomposition)
Yb(NTF 2) 3 270
This vacuum deposition processes has already obtained application at microelectronics and semi-conductor.Vacuum deposition method is suitable for any metal that decomposes two (fluoroform sulphonyl) group with imine moiety before boiling.
The present invention also provides a kind of method of preparation metal two of the present invention (fluoroform sulphonyl) group with imine moiety, and this method comprises to be made:
(a) two (fluoroform sulphonyl) imines and metal reaction;
(b) two (fluoroform sulphonyl) imines and metal peroxides reaction;
(c) two (fluoroform sulphonyl) imines and metallic sulfide reaction; Or
(d) two (fluoroform sulphonyl) imines and metal carbonate reaction.
This method is suitable for preparing metal two of the present invention (fluoroform sulphonyl) group with imine moiety and known metal two (fluoroform sulphonyl) group with imine moiety.So aforesaid method can be used for wherein, and M is metal two (fluoroform sulphonyl) group with imine moiety that is selected from the metal of periodic table of elements 1-16 family and lanthanide series metal and actinide metals.
Preferred aforesaid method comprises metal or metallic compound and two (fluoroform sulphonyl) imines (i.e. (two (fluoroform sulphonyl) imines (bis-trifluoromethanesulfonimide) or HN (SO 2CF 3) 2) react to each other.Preferred described metal is transition metal (d district or f district) or the metal that is selected from 12 to 16 families.Preferred described metal is selected from Sn (IV), Fe (III), In (III), Hf (IV), Ti (IV) and W (VI).
Described method can be carried out in solvent such as water, alcohol, ester or molecule supercritical solvent such as carbonic acid gas or ion solvent.Described reaction can be carried out under room temperature or high temperature.If also can reacting to each other under solvent-free by two (fluoroform sulphonyl) imines and metallic compound, use solvent, described metal two (fluoroform sulphonyl) group with imine moiety prepare.Metal two (fluoroform sulphonyl) group with imine moiety can by solvent evaporation (usually by heating removing water or other solvent, and preferably under vacuum, carry out) and separated from solvent.Further purifying can be undertaken by the vacuum distilling or the vacuum-sublimation of metal two (fluoroform sulphonyl) group with imine moiety.Also can be by some other physics or chemical process such as crystallization carry out purifying.
Be used for catalyzed chemical reaction after metal two of the present invention (fluoroform sulphonyl) group with imine moiety can prepare on the spot or cause chemical transformation.This comprises metallic compound (such as metal halide such as muriate, bromide, iodide or fluorochemical) is joined in two (fluoroform sulphonyl) imines ion source (such as two (fluoroform sulphonyl) imines ion liquid).Preferred described metallic compound is a metal chloride.These metals that prepare on the spot two (fluoroform sulphonyl) group with imine moiety has than the higher or similar catalytic activity of isolating metal two (fluoroform sulphonyl) group with imine moiety.Therefore the present invention provides a kind of method for preparing metal two (fluoroform sulphonyl) group with imine moiety, this method to comprise to two (fluoroform sulphonyl) imines ion source to add metal or metallic compound in such as two (fluoroform sulphonyl) imines ion liquid.Ionic liquid is to be in the liquid melting salt or the mixture of salt under temperature of reaction.Ionic liquid comprises two kinds of components: the positively charged ion of positive charge and the negatively charged ion of negative charge.Preferred described positively charged ion is an organic cation, and negatively charged ion is the organic or inorganic negatively charged ion.The positively charged ion that is used for described method be preferably the 1-alkyl pyridine _ (as 1-hexyl pyridine _) or 1,3-dialkylimidazolium _ positively charged ion such as 1-butyl-3-Methylimidazole _ [bmim] or 1-ethyl-3-Methylimidazole _ [emim].Other positively charged ion that is used for present method have other alkyl-or many alkyl pyridines _, alkyl or many alkyl imidazoles _, alkyl or many alkyl pyrazoles _, alkyl or many alkylammoniums, alkyl or many alkyl _ positively charged ions, other ammonium, _ positively charged ion, alkylation diazabicyclo-[5,4,0]-and 11 carbon-7-alkene and relevant positively charged ion, or any other produces the positively charged ion of so-called ion liquid compound.The negatively charged ion that is used for the inventive method is preferably the negatively charged ion of in reaction chemical transformation being stablized and given the required physical features of ionic liquid.Some negatively charged ion that are suitable for described ionic liquid have two-fluoroform sulfimide, two-five fluorine second sulfimides, hexafluoro-phosphate radical (V), tetrafluoroborate (III), the trifluoromethanesulfonic acid root, cyanamide, fluoro or perfluoro alkyl sulfonic acid root, halogenide, sulfate radical, bisulfate ion, alkyl sulfate, alkyl azochlorosulfonate, the aromatic sulfuric acid root, the aryl sulfonic acid root, nitrate radical, carboxylate radical, phosphate radical, hydrogen phosphate, dihydrogen phosphate, the alkylphosphonic acid carboxylic acid root, the alkylphosphines acid group, phosphonate radical, nitrite anions, arsenate, the metaantimmonic acid root, the halogenated aluminum acid group, aluminate, borate, silicate, haloindate (III), the gallic acid root, the boron alkyl acid group, other negatively charged ion of halo gallic acid root or any generation ionic liquid.Preferred described ionic liquid or described catalyzer or described ionic liquid and catalyst composition are insoluble to low polarity or non-polar organic solvent such as diethyl ether or hexane.
The example of preformed two (fluoroform sulphonyl) imine catalyst and the catalyzer that forms with Benzoyl chloride acidylate toluene on the spot is as follows:
Figure C0280942100101
In this reaction, because product (a kind of ketone) forms strong complex and makes its similar passivation with iron(ic) chloride (III), iron(ic) chloride (III) is with the described reaction of not catalysis (obtaining low-down yield).Iron(ic) chloride (III) is joined two (fluoroform sulphonyl) imines source (two (fluoroform sulphonyl) imines { HN (SO 2CF 3) 2) or two (fluoroform sulphonyl) inferior amine salts or ionic liquid cause the formation of two (fluoroform sulphonyl) imines iron (III) complex compounds (or chloro two (fluoroform sulphonyl) imines iron (III) compound or complex compound).These fluoroform sulfimide iron (III) complex compounds (or chloro two (fluoroform sulphonyl) imines iron (III) compound or complex compound) can be used as the catalyzer as chemical reactions such as acidylates then.The speed of the reaction in the above-mentioned reaction icon is close, and high yield (99%) is provided.
This catalyzer that can be used for the synthetic of metal trifluoroacetate methylsulfonyl group with imine moiety and use is the feasible metal useful as catalysts of seldom following the friedel-crafts chemical reaction of synthetic method on the spot.Also can prepare and be difficult to isolating two (fluoroform sulphonyl) group with imine moiety and used as catalyzer.
In many cases, form the method that the method for metal two (fluoroform sulphonyl) group with imine moiety is better than separating described metal trifluoroacetate methylsulfonyl group with imine moiety on the spot.For example, two (fluoroform sulphonyl) imines tin (IV) are a kind of isolated compound that is difficult to.If tin chloride (IV) is dissolved in fluoroform sulfimide ionic liquid ([bmim] [NTf for example 2]) in, but the mixture catalysis friedel-crafts acylation reaction that then obtains.This can be referring to Fig. 4, and Fig. 4 has shown that the yield of metal trifluoroacetate methylsulfonyl group with imine moiety (embodiment 45-50) of form on the spot of five kinds of catalysis Benzoyl chlorides and reaction of toluene is to time curve.
The present invention will illustrate with the following examples.Embodiment 1 to 26 is the reactive example of new metal two of the present invention (fluoroform sulphonyl) group with imine moiety.Embodiment 27 to 50 is the method for preparation metal two of the present invention (fluoroform sulphonyl) imine catalyst.
The yield that Fig. 1 has shown metal two catalytic Benzoyl chloride of (fluoroform sulphonyl) imines and reaction of toluene over time.
Fig. 2 has shown 1%FeCl 3Catalytic with 1% 2 (fluoroform sulphonyl) imines Fe (III) at [bmim] [NTf 2] in Benzoyl chloride and the yield of reaction of toluene over time.
Fig. 3 has shown the synthetic middle yield of phenyl-4-chloro-phenyl-sulfone over time.
Fig. 4 has shown that five are dissolved in [bmim] [NTf by 1% (mole) 2] in metal chloride catalyticly form in the reaction of methyldiphenyl ketone yield over time at 110 ℃ of Benzoyl chlorides and toluene.
Fig. 5,6 and 7 has shown Zn (NTf 2) 2Structure.
Embodiment 1: the reaction of toluene and Benzoyl chloride in the presence of two (fluoroform sulphonyl) imines cobalts (II)
At the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger 3In the round-bottomed flask, with two (fluoroform sulphonyl) imines cobalts (II) (0.13g, 0.21mmol) join toluene (3.0g, 32.5mmol) and Benzoyl chloride (3.0g, 21.3mmol) in.Mixture heating up is refluxed 3 hours (finishing at least 99% by gas chromatographic analysis judgement reaction) postcooling to room temperature.Add sherwood oil (15cm 3, bp=40-60 ℃) catalyzer is precipitated out from solution.Decantation product solution is also used 15cm again 3The petroleum ether flask.From the petroleum ether extraction liquid evaporating solvent that merges and the Kugelrohr apparatus device vacuum distilling purified product (bp=160-170 ℃ @1mmHg).This has formed methyldiphenyl ketone (4.05g, 97% separation yield).Reaction repeated can recycle described catalyzer immediately in the flask (throw out is housed) by toluene and Benzoyl chloride are joined.
Embodiment 2: in the presence of two (fluoroform sulphonyl) imines cobalts (II) in [emim] [NTf 2] in the toluene that carries out and the reaction of Benzoyl chloride
At the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger 3In the round-bottomed flask, (0.13g 0.21mmol) joins 1-ethyl-3-Methylimidazole _ ([emim] [NTf with two (fluoroform sulphonyl) imines cobalts (II) 2) (2.0g) in, stir the mixture up to dissolving.Add toluene (3.0g, 32.5mmol) and Benzoyl chloride (3.0g, 21.3mmol).Mixture heating up is refluxed 0.5 hour (finishing at least 99% by gas chromatographic analysis judgement reaction) postcooling to room temperature.Add sherwood oil (15cm 3, bp=40-60 ℃) and formation separates phase with ionic liquid to make catalyzer.Decantation product solution is also used 15cm again 3Petroleum ether flask (ionic liquid and catalyzer are housed) three times.From the petroleum ether extraction liquid evaporating solvent that merges and the Kugelrohr apparatus device vacuum distilling purified product (bp=160-170 ℃ @1mmHg).This has formed methyldiphenyl ketone (4.02g, 96%).Reaction repeated can recycle described catalyzer immediately and the ionic liquid composition does not have active loss by toluene and Benzoyl chloride being joined in the flask.
Embodiment 1 and 2 has shown that the acidylate of the toluene that carries out with Benzoyl chloride can carry out with two (fluoroform sulphonyl) imines cobalt (II) catalyzer, and its can ionic liquid exist or not in the presence of carry out.But if there is ionic liquid, then can obtaining faster, reactivity also can more easily recycle catalyzer.If there is no ionic liquid then can obtain reaction product with 1% (mole) catalyzer (embodiment 1) with quantitative yield after 3 hours in reflux.When being reflected at ionic liquid [emim] [NTf 2] when ([emim]=1-ethyl-3-Methylimidazole _) carried out under existing, the reaction times can reduce to 30 minutes (embodiment 2).
Embodiment 3: at [emim] [NTf 2] toluene that carries out with two (fluoroform sulphonyl) imines nickel (II) catalyzer and the reaction of Benzoyl chloride
At the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger 3In the round-bottomed flask, (0.13g 0.21mmol) joins 1-ethyl-3-Methylimidazole _ two (fluoroform sulphonyl) imines ([emim] [NTf with two (fluoroform sulphonyl) imines nickel (II) 2]) (2.0g) in, stir the mixture up to catalyst dissolution.Add toluene (3.0g, 32.5mmol) and Benzoyl chloride (3.0g, 21.3mmol).Mixture heating up is refluxed 1 hour (finishing at least 99% by gas chromatographic analysis judgement reaction) postcooling to room temperature.Add sherwood oil (15cm 3, bp=40-60 ℃) and formation separates phase with ionic liquid to make catalyzer.Decantation product solution is also used 15cm again 3Petroleum ether flask (ionic liquid and catalyzer are housed) three times.From the petroleum ether extraction liquid evaporating solvent that merges and the Kugelrohr apparatus device vacuum distilling purified product (bp=160-170 ℃ @1mmHg).This has formed methyldiphenyl ketone (4.04g, 97% separation yield).Reaction repeated can recycle described catalyzer immediately and the ionic liquid composition does not have active loss by toluene and Benzoyl chloride being joined in the flask.
Embodiment 2 and 3 the results are shown in the table 1.
Table 1: by Benzoyl chloride and toluene in [emim] [NTf 2] in the presence of 1% metal two (fluoroform sulphonyl) imine catalyst gas-chromatography (GC) yield of the benzophenone that obtains of reaction
Compound Yield Time (hour)
Co(NTf 2) 2 99 0.5
Ni(NTf 2) 2 99 1
Embodiment 4
With methyl-phenoxide (0.30cm 3, 2.8mmol), diacetyl oxide (0.50cm 3, 5.0mmol), M (NTf 2) nCatalyzer (0.1375mmol (M=Al, n=3; M=Zn, n=2; M=Yb, n=3; M=Y n=3) is dissolved in ionic liquid (bmim) [PF 6] in.These four kinds of reactants were heated 24 hours down at 30 ℃.HPLC by reaction mixture analyzes the monitoring reaction process, and its yield is shown in table 2.
Table 2: at [bmim] [PF 6] in the GC yield of metal two (fluoroform sulphonyl) methyl-phenoxide that imine catalyst carries out and the acylation reaction of diacetyl oxide over time
Catalyzer % yield (35 minutes) % yield (115 minutes) % yield (245 minutes) % yield 1375 minutes)
Al(NTf 2) 3 45 55 61 63
Zn(NTf 2) 3 23 36 44 61
Yb(NTf 2) 3 49 61 64 69
Y(NTf 2) 3 55 62 71
Embodiment 5
With methyl-phenoxide (0.50cm 3, 4.6mmol), benzoyl oxide (1.15g, 5.06mmol), M (NTf 2) nCatalyzer (0.23mmol (M=Al, n=3,0.20g; M=Ce, n=4 0.29g) is dissolved in ionic liquid (bmim) [NTf 2] (2.0g) in.These two kinds of reactants were heated 24 hours down at 60 ℃.By the GC assay determination reaction process of reaction mixture, its yield is shown in table 3.
Table 3: at [bmim] [PF 6] the middle GC yield that reacts with metal two (fluoroform sulphonyl) methyl-phenoxide that imine catalyst carries out and the benzoylation of benzoyl oxide over time
Catalyzer % yield (60 minutes) % yield (120 minutes) % yield (180 minutes) % yield (1350 minutes)
Al(NTf 2) 3 44 62 67 68
Ce(NTf 2) 4 32 49 56 84
Embodiment 6
With fluorobenzene (5.77g, 60mmol), the 4-fluorobenzoyl chloride (4.75g, 30mmol), ZnCl 2(1.36g is 10mmol) with [emim] [NTf 2] place autoclave and 160 ℃ of stirring heating 48 hours.With reactor cooling and relief pressure (HCl gas).Gas chromatographic analysis show with 99% transformation efficiency form 2,4 ' difluoro benzophenone, 3,4 that ratio was respectively 17: 8: 75 '-difluoro benzophenone and 4,4 '-mixture of difluoro benzophenone.By separating described difluoro benzophenone, follow solvent evaporated with sherwood oil (bp=40-60 ℃) extraction solvent.Described ionic liquid/zinc chloride catalyst system can suitable activity be used further to reaction.This result shows that inactive traditionally aromatic substance fluorobenzene can use on the spot zinc catalyst at [emim] [NTf 2] middle with 4-fluorobenzoyl chloride acidylate formation 2-, 3-, or 4-, 4 '-the difluoro benzophenone isomer.This catalyzer is by being dissolved in [emim] [nTf with zinc chloride (II) 2] form in the ionic liquid.Described reaction have 95% yield (17: 8: 75 neighbours-,, to isomer ratio).
Embodiment 7
With phenylformic acid (0.31g, 2.5mmol), m-xylene (0.53g, 5.0mmol), [bmim] [NTf 2] (0.50g) and M (NTf 2) 2(M=Co (and 0.14g, 0.25mmol) or Zn (0.15g, 0.25mmol)) place the flask of being furnished with agitator and condenser.Reflux flask contents (about 140-150 ℃) 2 days, cool to room temperature then.Find respectively that by the gas chromatographic analysis product transformation efficiency (respectively for two (fluoroform sulphonyl) imines cobalts and zinc reaction) with 93% and 87% forms 2,4-dimethyl benzophenone and believe it is 2,6-dimethyl benzophenone (being 11: 1 isomer ratios in both cases).The result shows that two (fluoroform sulphonyl) imines zinc and cobalt can catalysis m-xylene and the reactions of benzoic benzoylation.This reaction is slower than the reaction of corresponding and Benzoyl chloride.Catalyst recirculation is used reaction repeated.Repeated experiments the results are shown in table 4.
Table 4: phenylformic acid and m-xylene at 140 ℃ of metals two (fluoroform sulphonyl) imine catalyst with 10% recycle in [bmim] [NTf 2] the middle yield that reacts the benzophenone that formed in 48 hours.
Compound The % yield 2,4-and 2, the ratio of 6-
Zn(NTf 2) 2 40 11∶1
Co(NTf 2) 2 82 11∶1
These provide the SA important results of phenylformic acid.Should point out that this reaction produces as the water of by product and therefore it is a kind of reaction of very environmental protection.In addition, this reaction is used non-aggressive raw material (phenylformic acid) and therefore is than carrying out corresponding and the safer reaction of reaction Benzoyl chloride.Can think that it is the excellent approach of preparation dimethyl benzophenone.
Embodiment 8: the toluene that carries out in [emim] [NTf2] with two (fluoroform sulphonyl) imines zinc (II) or copper (II) catalyzer and the reaction of Benzoyl chloride
With two (fluoroform sulphonyl) imines copper or zinc (II) (0.13g, 0.21mmol) join toluene (3.0g, 32.5mmol) and Benzoyl chloride (3.0g is in mixture 21.3mmol).With mixture reflux 72 hours (coming monitoring reaction by gas chromatographic analysis behind the filtration catalizer) by getting a reaction mixture and it being suspended in the sherwood oil (bp=40-60 ℃).The raw material and the product cool to room temperature of petroleum ether extract will be dissolved in.Add sherwood oil (15cm 3, bp=40-60 ℃) and make catalyzer form independent phase.Decantation product solution is also used 15cm with flask (catalyzer is housed) 3Petroleum ether three times.From the petroleum ether extract that merges evaporating solvent and with product by vacuum distilling in the Kugelrohr apparatus device (bp=160-170 ℃ @1mmHg) purified product.Thereby form methyldiphenyl ketone (4.0g, 95%).Can recycle catalyzer immediately and do not have active loss by add toluene and Benzoyl chloride and reaction repeated to flask.The yield that gas chromatographic analysis records is listed in table 5.
Table 5: Benzoyl chloride and toluene react the yield of the benzophenone that forms in the presence of 1% 2 (fluoroform sulphonyl) imines copper (II) or 1% 2 (fluoroform sulphonyl) imines zinc (II) catalyzer.Numeral in the bracket be meant the neighbour-,-and right-isomer ratio
Time (hour) With Zn (NTf 2) 2Yield With Cu (NTf 2) 2Yield
24 83 52
48 99(22∶1∶77)
72 99(20∶2∶78)
Find that two (fluoroform sulphonyl) imines zinc (II) and copper (II) are the benzoylated effective acylation catalysts of toluene.
Embodiment 9: the reaction in the presence of two (fluoroform sulphonyl) imines aluminium (III) catalyzer of o-Xylol and Benzoyl chloride
With two (fluoroform sulphonyl) imines aluminium (III) (0.10g) join o-Xylol (3.0g, 28.2mmol) and Benzoyl chloride (3.0g is in mixture 21.3mmol).With mixture 120 ℃ of heating 18 hours (by after getting a reaction mixture and it being suspended in sherwood oil (bp=40-60 ℃) and filtration catalizer by the gas chromatographic analysis monitoring reaction.Raw material and product dissolve in the petroleum ether extraction liquid) and cool to room temperature.Add sherwood oil (15cm 3) and catalyzer form independent phase.The yield that gas chromatographic analysis records is 99%, its 3,4-and 2, the ratio of 3-dimethyl benzophenone isomer is 6.0: 1.Find that two (fluoroform sulphonyl) imines aluminium (III) are the benzoylated effective catalysts of o-Xylol.Use the catalyzer of 1% (mole), after 18 hours, described reaction provides the isomer (6: 13,4-and 2,3-isomer ratio) of two kinds of corresponding benzophenone of quantitative yield 120 ℃ of reactions.
Embodiment 10: the toluene that carries out with metal two (fluoroform sulphonyl) imine catalyst and the reaction of Benzoyl chloride
Various metals (1-ethyl-3-Methylimidazole _, Li, Mg, Ca, Mn, Co, Ni, Cu, Zn, Sn, Pb, Al) two (fluoroform sulphonyl) inferior amine salt (1% (mole)) is joined toluene (3.0g, 32.6mmol) and Benzoyl chloride (3.0g is in mixture 21.3mmol).This mixture was heated maximum 120 hours at 110 ℃.By gas chromatographic analysis at certain intervals monitoring reaction and when judging that reaction finishes 99% by the cool to room temperature stopped reaction.Add sherwood oil (15cm 3) and catalyzer form independent phase.By decantation petroleum ether extraction liquid, then pass through at 1mmHg Kugenrohr fractionation by distillation product.Yield after each timed interval is listed in table 6.The product that forms is a methyldiphenyl ketone.In all these reactions, find that isomer ratio is about 76% contraposition and 24% ortho position.This results are shown in table 6.Table 1 has been listed two (fluoroform sulphonyl) imines Co and Ni at [emim] [NTf 2] in the required time.
Table 6: the yield of the benzophenone that Benzoyl chloride that carries out with 1% metal two (fluoroform sulphonyl) imine catalyst and reaction of toluene obtain
Compound Yield (%) Time (hour)
[emim]{NTf 2] ＜1 48
LiNTf 2 ＜5 120
Mg(NTf 2) 2 99 48
Ca(NTf 2) 2 ＜5 120
Mn(NTf 2) 2 99 5
Co(NTf 2) 2 99 3
Ni(NTf 2) 2 99 4
Cu(NTf 2) 2 99 72
Zn(NTf 2) 2 99 48
Sn(NTf 2) 2 55 48
Pb(NTf 2) 2 95 6
Al(NTf 2) 3 99 24
Observe from table 6 that there is significant difference in reactivity between selected compound.Wherein, four kinds of compound exhibits go out to have unusual high reactivity, i.e. two (fluoroform sulphonyl) imines manganese, cobalt, nickel and lead, and compound has relative moderate activity as two (fluoroform sulphonyl) imines zinc and two (fluoroform sulphonyl) imines aluminium.This is diverse with " conventional friedel-crafts chemistry " (it thinks that two (fluoroform sulphonyl) imines aluminium should be best catalyzer).It should be noted that the catalytic activity of Co and Pb especially.Two (fluoroform sulphonyl) imines lithium is opposite with calcium, demonstrates low-down activity and observes and not reaction or few reaction of [emim] [two (fluoroform sulphonyl) imines].
Embodiment 11: at [bmim] [NTf 2] in the chlorobenzene that carries out with two (fluoroform sulphonyl) imines nickel (II) and the reaction of Benzoyl chloride
(0.062g 0.1mmol) joins at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger with two (fluoroform sulphonyl) imines nickel (II) 3In the round-bottomed flask two (fluoroform sulphonyl) imines 1-butyl-3-Methylimidazole _ ([bmim] [NTf 2]) (1.0g) in, and stir to mix compound up to catalyst dissolution.Add chlorobenzene (1.68g, 15mmol) and benzoyl fluoride (1.41g, 10mmol).The mixture heating up backflow was also measured by gas chromatographic analysis in 72 hours as in the previous examples.With the reactant cool to room temperature.Add sherwood oil (15cm 3, bp=40-60 ℃) and catalyzer form mutually independent from petroleum ether layer with ionic liquid.Decantation product solution (in sherwood oil) is also used 15cm 3Petroleum ether flask (ionic liquid and catalyzer are housed) three times.Concentrate organic extract liquid, then, obtain chloro benzophenone (1.65g, 74%) in 1mmHg (bp=170-190 ℃) Kugenrohr distillation down.The GC analysis revealed obtains 78% yield after 72 hours, and 4-and 2-isomer ratio are 70: 8.This is an important result, because known chlorobenzene is inactive to acylation reaction traditionally.Previous and the impossible acylate that separates a large amount of chlorobenzenes.
Embodiment 12: chlorobenzene and Benzoyl chloride with two (fluoroform sulphonyl) imines cobalts (II) or two (fluoroform sulphonyl) imines zinc (II) at [bmim] [NTf 2] in the reaction carried out.
In two independent reactions, two (fluoroform sulphonyl) imines zinc (II) (0.16g, 5% (mole)) or two (fluoroform sulphonyl) imines cobalts (II) (0.15g, 5% (mole)) are joined at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger 3In the round-bottomed flask two (fluoroform sulphonyl) imines 1-butyl-3-Methylimidazole _ ([bmim] [NTf 2]) (1.0g) in, with the mixture mild heat and stir up to catalyst dissolution.Add chlorobenzene (0.68g, 6mmol) and Benzoyl chloride (0.72g, 5mmol).Mixture heating up is refluxed 18 hours also as in the previous examples by gas chromatographic analysis.With the reactant cool to room temperature.Add hexanaphthene (15cm 3) and catalyzer form mutually independent with ionic liquid.Decantation product solution is also used 15cm 3Hexanaphthene washing flask (ionic liquid and catalyzer are housed) three times also then distills (bp=180-200 ℃) at 1mmHg Kugelrorh.Form the mixture of 2-and 4-chloro benzophenone.The GC yield is 97% (ratio of contraposition in 6.8: 1 and ortho isomer) for cobalt catalyst, and the GC yield is 55% (contraposition in 6.5: 1 and ortho isomer ratio) for zinc catalyst.
The reaction of research chlorobenzene and Benzoyl chloride is because chlorobenzene more is difficult to acidylate.Though can obtain sizable yield with 1% (mole) catalyzer, find that 5% (mole) catalyzer provides more acceptable response speed.Find to finish 95% at 18 hours afterreactions, finished 55% (table 7) with two (fluoroform sulphonyl) imines zinc with two (fluoroform sulphonyl) imines cobalt.Discovery is reducing activity with boiling cyclohexane extraction product and the ionic liquid that circulates/catalyzer rear catalyst.Recovered activity of such catalysts by adding trace two (fluoroform sulphonyl) imines (0.1% (mole)).
Table 7: Benzoyl chloride and chlorobenzene are at [bmim] [NTf 2] in react the yield of the benzophenone of acquisition with 5% metal two (fluoroform sulphonyl) imine catalyst
Compound Yield Time (hour)
Co(NTf 2) 2 95 18
Zn(NTf 2) 2 55 18
Embodiment 13: the toluene that carries out with hydrogen and metal two (fluoroform sulphonyl) imine catalyst and the reaction of Benzoyl chloride
With various metals two (fluoroform sulphonyl) group with imine moiety: Sr (II), Ba (II), In (III), at [bmim] [NTf 2] in In (III), Cr (III), Ce (IV), Yb (III) and two (fluoroform sulphonyl) imines { HN (SO 2CF 3) 2(1% (mole)) join toluene (1.38g, 15.0mmol) and Benzoyl chloride (1.41g is in mixture 10.0mmol).Mixture was heated maximum 120 hours at 110 ℃.By gas chromatographic analysis with the different interval monitoring reaction and after 5 days stopped reaction.The yield of methyldiphenyl ketone corresponding to the curve display of time in Fig. 1.Benzoyl chloride and reaction of toluene have formed 2-and 4-methyldiphenyl ketone.Find that all these compounds all are active catalysts of Friedel-Crafts reaction, but have significantly different activity.Wherein, the activity of indium (III) and iron (III) (embodiment 14) is introduced attention most, because they are good unusually catalyzer.Contraposition and adjacent selectivity are in 3.9 to 4.4 to 1 scope, and indium and iron catalyst provide 4.4: 1 selectivity.
Embodiment 14: with two (fluoroform sulphonyl) imines iron (III) or be dissolved in [bmim] [NTf 2] iron(ic) chloride (III) Benzoyl chloride and the reaction of toluene of carrying out
In two independent reactions, two (fluoroform sulphonyl) imines iron (III) (1% (mole)) or iron(ic) chloride (III) (1% (mole)) are joined at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger 3Two-fluoroform sulfimide 1-butyl-3-Methylimidazole _ ([bmim] [NTf in the round-bottomed flask 2]) (1.0g) in, with the mixture mild heat and stir up to catalyst dissolution.Add toluene (1.38g, 15mmol) and Benzoyl chloride (1.41g, 10mmol).Mixture heating up refluxed 48 hours and as described above embodiment measure by gas chromatographic analysis like that.The yield of methyldiphenyl ketone with respect to the curve display of time in Fig. 2.Here, measure the activity of iron catalysts with two kinds of different modes: (a) with 1% at [bmim] [NTf 2] in FeO (NTf 2) carry out and (b) 1% at [bmim] [NTf 2] in FeCl 3Carry out.In both cases, activity and selectivity are all similar, show FeCl 3And FeO (NTf 2) be dissolved in excessive [bmim] [NTf 2] time all may be the precursor of catalyzer.
Embodiment 15: the toluene that carries out with two (fluoroform sulphonyl) imines zinc (II) and the reaction of methane sulfonyl chloride
Two (fluoroform sulphonyl) imines zinc (II) (0.13g, 2.5% (mole)) are joined in the round-bottomed flask of being furnished with magnetic stirring apparatus and reflux exchanger.Add toluene (1.38g, 15mmol) and methylsulfonyl chloride (1.14g, 10mmol).The mixture heating up backflow was also measured by gas chromatographic analysis in 24 hours as in the previous examples.All methylsulfonyl chlorides all react and have formed three kinds of isomer (yield is 99%) of (2-, 3-and 4-aminomethyl phenyl) methyl sulfone, and ortho position, a position and para-isomeride ratio are 35: 18: 47.By being dissolved in hexanaphthene (20cm 3) in and then decantation cyclohexane extract liquid from the catalyst extraction product.With hexanaphthene (2 * 20cm 3) washing catalyst and the concentrated cyclohexane extract liquid that merges on rotatory evaporator.Obtain 1.62g water white oil (96% separation yield) at 100-110 ℃ of Kugelrohr product of distillation.
Embodiment 16: the benzene that carries out with two (fluoroform sulphonyl) imines zinc (II) and the reaction of benzene sulfonyl chloride
Two (fluoroform sulphonyl) imines zinc (II) (0.062g, 1% (mole)) are dissolved in [bmim] [NTf in a round-bottomed flask of being furnished with magnetic stirring apparatus and reflux exchanger 2] (1.0g) in.Add benzene (1.56g, 20mmol) and benzene sulfonyl chloride (1.76g, 10mmol).The mixture heating up backflow was also measured by gas chromatographic analysis in 18 hours as in the previous examples.All benzene sulfonyl chlorides all react and form sulfobenzide (yield is 99%).By being dissolved in boiling cyclohexane (5 * 30cm 3) in and then decantation cyclohexane extract liquid from catalyzer and ionic liquid extraction product.Sulfobenzide is collected (2.03g, 93% separation yield) through crystallisation by cooling and by filtering.With Zn (NTf 2) 2The benzene that catalyzer carries out and the reaction of benzene sulfonyl chloride have obtained the sulfobenzide (refluxing 18 hours) of expection with 99% yield.Extract sulfobenzide and recycle ionic liquid and catalyzer with boiling cyclohexane.
Embodiment 17: the m-xylene that carries out with two (fluoroform sulphonyl) imines zinc (II) and the reaction of benzene sulfonyl chloride
Two (fluoroform sulphonyl) imines zinc (II) (0.062g, 1% (mole)) are dissolved in [the bmim] [NTf that places the round-bottomed flask dress of being furnished with magnetic stirring apparatus and reflux exchanger 2] (1.0g) in and add m-xylene (2.12g, 20mmol) and benzene sulfonyl chloride (1.76g, 10mmol).The mixture reflux was also carried out gas chromatographic analysis in 18 hours as in the previous examples to be measured.All benzene sulfonyl chlorides have all reacted and have mainly formed 2,4-dimethyl diphenyl sulfone (yield is 99%, and isomer ratio is 20: 1{NMR measures }).Principal product is as follows, structure the unknown of minor isomer, but believe it is 2,6-dimethyl isomer.
Figure C0280942100221
By being dissolved in boiling cyclohexane (5 * 30cm 3) in and then decantation hexanaphthene extraction liquid come extraction product from catalyzer and ionic liquid.With 2,4-dimethyl diphenyl sulfone crystallisation by cooling also passes through to filter and collects.
Embodiment 18: the chlorobenzene that carries out with metal two (fluoroform sulphonyl) imine catalyst and the reaction of benzene sulfonyl chloride
In three are independently reacted, with two (fluoroform sulphonyl) imines magnesium (II) (0.058g, 0.1mol), two (fluoroform sulphonyl) imines aluminium (III) (0.87g, 0.1mmol) or two (fluoroform sulphonyl) imines cobalts (II) (0.062g 0.1mmol) is dissolved in [the bmim] [NTf that places the round-bottomed flask of being furnished with magnetic stirring apparatus and reflux exchanger 2] (0.5g) in.Add chlorobenzene (1.68g, 15mmol) and benzene sulfonyl chloride (1.76g, 10mmol).The mixture heating up backflow was also monitored by gas chromatographic analysis in 144 hours as in the previous examples.Yield and time relation figure list among Fig. 3.By being dissolved in boiling cyclohexane (4 * 10cm 3) also then decantation hexanaphthene extraction liquid extracts product from catalyzer and ionic liquid.2-and 4-chloro-diphenyl sulfone (ratio of contraposition in 9: 1 and ortho isomer) crystallisation by cooling are also collected by filtering.The selectivity of contraposition and ortho isomer is 9: 1, and ortho isomer all is less important isomer in all cases.Simultaneously, the reaction of Benzoyl chloride and chlorobenzene also has similar selectivity and speed of reaction.Phenyl-4-sulphenone is a kind of sterilant.Sluggish when finding to use 1% (mole) catalyzer, but be to use 5% (mole) catalyzer just to obtain acceptable response speed.Selected metal-salt is at ionic liquid [bmim] [NTf 2] in two (fluoroform sulphonyl) imines aluminium (III), cobalt (II) and magnesium (II).Find that all these three kinds of catalyzer are the effective catalyst of this reaction.Described reaction is as follows:
Figure C0280942100231
Embodiment 19: the benzene that carries out with two (fluoroform sulphonyl) imines nickel (II) and the reaction of suffering-1-alkene
(0.06g 0.1mmol) is dissolved in [the bmim] [NTf that places the round-bottomed flask of being furnished with magnetic stirring apparatus and reflux exchanger with two (fluoroform sulphonyl) imines nickel (II) 2] (1.0g) in.Add benzene (3.90g, 50mmol) and suffering-1-alkene (1.12g, 10mmol).The mixture heating up backflow was also monitored by gas chromatographic analysis in 18 hours as in the previous examples.The ratio of 26: 54 2-:3-:4-isomer) and octene dipolymer (30%) suffering-1-alkene peak disappears and has formed the isomer (70%, 20: of three kinds of octyl group benzene.The product rarer from ionic liquid/catalyzer phase decantation also passes through the Kugelrohr apparatus distillation purifying mutually.With ionic liquid and catalyzer by recycling after 1 hour in heating under 60 ℃ of vacuum.Ionic liquid and catalyzer can be further used for the reaction of benzene and suffering-1-alkene and not have active loss.This is the benzene that carries out of a kind of use metal two (fluoroform sulphonyl) imine catalyst and the alkylated reaction of alkene.Reaction forms isomer and a small amount of cetene (unknown isomeric distribution) of three kinds of octyl group benzene in the presence of 1% 2 (fluoroform sulphonyl) the imines nickel (II) of benzene and suffering-1-alkene in [bmim] [NTf2].React as follows:
The alkylation of benzene and suffering-1-alkene
Described reaction obtains three kinds of octyl group benzene isomer of 70% yield (GC mensuration).Isomer ratio is 0.75: 1.00: 2.03 after measured, and principal product is a 4-phenyl octene, and inferior product is a 2-phenyl octene.In reaction process, to observe suffering-1-bisabolene isomer and become various octene isomers, the speed ratio alkylated reaction speed of this isomate process is faster.Find that ionic liquid/catalyst composition still keeps active when going on a long journey for the second time.For the inferior product that confirms to react is the octene dipolymer, do not having to carry out identical reaction (as follows) in the presence of the benzene
The dimerization of suffering-1-alkene
Reaction is the mixture that the octene isomery becomes 4 kinds of octane isomers at first.After 18 hours, (＞95% transformation efficiency) almost finished in reaction.Product is the isomer of a large amount of dimerization and trimerization octene.Allow reaction carry out 6 days, observe dipolymer and trimer GC peak Shu Biankuan, show other isomery has taken place.
Embodiment 20: the dimerization of the suffering-1-alkene that carries out with two (fluoroform sulphonyl) imines nickel (II)
(0.062g 0.1mmol) is dissolved in [the bmim] [NTf that places the round-bottomed flask dress of being furnished with magnetic stirring apparatus and reflux exchanger with two (fluoroform sulphonyl) imines nickel (II) 2] (0.5g) in.Adding suffering-1-alkene (1.12g, 10mmol).The mixture heating up backflow was also monitored by gas chromatographic analysis in 18 hours as in the previous examples.Find that suffering-1-alkene peak disappears and formed the isomer (oct-2-ene, suffering-3-alkene and suffering-4-alkene) of three kinds of octenes.(0.0028g is 0.1mmol) and with mixture reheat 18 hours to add two (fluoroform sulphonyl) imines.Gas chromatographic analysis shows reaction almost completely (＞99%), and has formed cetene and tetracosene (trimer of octene) mixture of isomers.From the rarer product of ion/catalyzer phase decantation mutually and under 1mmHg by the Kugelrohr apparatus distillation purifying.With ionic liquid and catalyzer by recycling after 1 hour in heating under 60 ℃ of vacuum.Ionic liquid and catalyzer are further used for the dimerization reaction of suffering-1-alkene and do not have active loss.
Embodiment 21: the Fries rearrangement of the 4-methylphenoxy benzoic ether that carries out with hydrogen and metal two (fluoroform sulphonyl) group with imine moiety
With two (fluoroform sulphonyl) imines ytterbiums (III) (0.1g) and two (fluoroform sulphonyl) imines (0.01g) be dissolved in [n-H in the round-bottomed flask of being furnished with magnetic stirring apparatus and reflux exchanger 29C 14(n-H 13C 6) 3P] [NTf 2] (1.0g) in.Add 4-methylphenoxy benzoic ether (1.0g).At 60 ℃ the mixture heating up backflow was also measured by gas chromatographic analysis in 24 hours as in the previous examples.Reaction product is a 2-hydroxy-5-methyl base benzophenone (90% yield).Shown that below 4-methylphenoxy benzoic ether becomes the isomerization reaction of 2-hydroxy-5-methyl base benzophenone.
Embodiment 22: o-Xylol, m-xylene, 1 and the toluene that carries out with metal two (fluoroform sulphonyl) group with imine moiety and the reaction of tetrahydrobenzene
In four independent reaction vessels, two (fluoroform sulphonyl) imines ytterbiums (III) (0.1g) are dissolved in [n-H in the round-bottomed flask of being furnished with magnetic stirring apparatus and reflux exchanger 29C 14(n-H 13C 6) 3P] [NTf 2] (2.0g) in.Respectively with o-Xylol (1.06g, 10mmol), m-xylene (1.06g, 10mmol), 1 (1.20g, 10mmol) and toluene (0.92g, 10mmol) join in separately the flask and then add tetrahydrobenzene (0.82g, 10mmol).Mixture was also carried out the gas chromatographic analysis monitoring in 12 hours as in the previous examples 80 ℃ of heating.Find that the tetrahydrobenzene peak disappears and formed the peak (referring to embodiment 26) that peak that the alkylation of described aromatic substance causes and tetrahydrobenzene dimerization reaction cause.By under vacuum, recycling ionic liquid and catalyzer after 1 hour in 60 ℃ of heating.Described ionic liquid and catalyzer are further used for the reaction of benzene and tetrahydrobenzene and do not have active loss.
Embodiment 23: with the reaction of metal two (fluoroform sulphonyl) imines, fluoroform sulphonate and the two catalytic benzene of (fluoroform sulphonyl) imines and 12 carbon-1-alkene
In ten independent reactors (the multicell glass reactor of tool agitator and condenser), metal trifluoroacetate methylsulfonyl imines or metal trifluoroacetate mesylate compound (referring to following table) are joined [n-H with two (fluoroform sulphonyl) imines (0.01g) 29C 14(n-H 13C 6) 3P] [NTf 2] (2.0g) in and be stirred to metallic compound dissolving.Add benzene (3.8g, 50mmol) and 12 carbon-1-alkene (0.84g, 5.0mmol).Mixture was heated 24 hours at 80 ℃.Distill excessive benzene.Behind the cool to room temperature mixture being carried out NMR analyzes.By under vacuum, recycling in 60 ℃ of heating preparation in 1 hour ionic liquid and catalyst supply.Described ionic liquid and catalyzer are further used for the reaction of benzene and 12 carbon-1-alkene and do not have active loss.It the results are shown in following table 8.
Table 8
Compound Quality (g) Unreacted dodecylene Isomerized dodecylene Dodecylbenzene
Yb(NTf 2) 3 1.02 0 0 100
Co(NTf 2) 2 0.62 0 99 1
Cu(NTf 2) 2 0.62 0 1 99
Pb(NTf 2) 2 0.76 0 100 0
In(NTf 2) 3 0.95 0 0 100
Ga(NTf 2) 3 0.63 0 61 39
Zn(OTf 2) 2 0.36 67 33 0
Cu(OTf 2) 2 0.36 1 96 3
Yb(OTf 2) 3 0.53 0 91 9
La(OTf 2) 3 0.59 0 60 40
Embodiment 24: with being dissolved in [bmim] [NTf 2] in the catalytic toluene of metallic compound and the reaction of Benzoyl chloride
In five independent reactors, titanium chloride (IV) (1% (mole)) or tin chloride (IV) (1% (mole)) or tungsten chloride (VI) or hafnium chloride (IV) or Palladous chloride (II) joined place the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger 3Two-fluoroform sulfimide 1-butyl-3-Methylimidazole _ ([bmim] [NTf in the round-bottomed flask 2]) (2.0g) in, add toluene (2.81g, 30mmol) and Benzoyl chloride (2.84g, 20mmol).With mixture reflux 24 hours and carry out gas chromatographic analysis monitoring as in the previous examples.Except the catalytic reaction of palladium (II) (75% yield), the equal Quantitative yield of raw material becomes methyldiphenyl ketone.In the reaction of Benzoyl chloride and toluene, in the reaction of several new metal two (fluoroform sulphonyl) inferior amine salts yield over time situation see Fig. 4.These react parallel carrying out, and yield is by the GC assay determination.Embodiment 45 to 50 provides this reaction more detailed situation.
In the present invention, the metal halide that is dissolved in two (fluoroform sulphonyl) imines ion liquid can be used for such as reactions such as friedel-crafts.This be difficult to preparation for metal two (fluoroform sulphonyl) inferior amine salt particularly or isolating situation particularly useful.In the present invention, five kinds of metal halides (muriate) (respectively being 1% (mole) of reactant) are dissolved in [bmim] [NTf 2] in.This composition is used to the reaction of catalysis toluene and Benzoyl chloride formation methyldiphenyl ketone.Yield is seen Fig. 4 to the curve of time.The metal of all selections all provides the product of expection with good yield, wherein at [bmim] [NTf 2] in the composition of 1% (mole) tin chloride (IV) be especially effective catalyzer.The method that use is dissolved in the metallic compound of ionic liquid (normally two (fluoroform sulphonyl) imines) also can be applicable to not list in the compound of other metal (particularly transition metal (d-district) or f-district metal) of Fig. 3 or 4.
Embodiment 25
Carry out numerous aromatic substance sulfonylations.These reactions are very similar to the friedel-crafts acylation reaction and carry out under conditions of similarity.Crucial difference is-SO 2-X base has replaced-CO-X (X=leavings group).As a rule, find that its selectivity, reactivity and yield are similar to corresponding acylation reaction.The reaction of SULPHURYL CHLORIDE and benzene causes chlorobenzene (quantitatively) and SO 2Formation.This and many SO 2Cl 2Identical with situation about finding in aromatic substance other reaction in molecular solvent.
Embodiment 26
Tool 10% 2 (fluoroform sulphonyl) imines ytterbium (III) and trace two (fluoroform sulphonyl) imines _ carry out the alkylation of various aromatic substance and tetrahydrobenzene in the ionic liquid.The side reaction (referring to following) of tetrahydrobenzene dipolymer has also taken place to produce, and this causes the slight decline of Friedel-Crafts reaction yield.But, should point out that this has proved that metal trifluoroacetate methylsulfonyl group with imine moiety can be used for dimerization and oligomerization.
Figure C0280942100291
Shown above aromatic substance and tetrahydrobenzene in _ ionic liquid 80 ℃ of reactions of carrying out 12 hours.The dimerization that has shown tetrahydrobenzene below.
Embodiment 27
The preparation of two (fluoroform sulphonyl) imines magnesium
(0.048g 2.0mmol) joins and places the 25cm that is furnished with magnetic stirring apparatus with magnesium 3In the round-bottomed flask two (fluoroform sulphonyl) imines (HN (SO 2CF 3) 2, 1.12g is in distilled water 4.0mmol) (5g) solution.Mixture is stirred 1 hour (then judging reaction when stopping when the hydrogen effusion finishes) after-filtration.Evaporating off water on rotatory evaporator, and by in Minton dryer under 150 ℃ of 1mmHg heat drying two (fluoroform sulphonyl) imines magnesium obtained white powder (1.10g, 95%) in 4 hours.By in Kugelrohr apparatus at 300 ℃ of following vacuum-sublimation purifying two of 1mmHg (fluoroform sulphonyl) imines magnesium.Find that unpurified two (fluoroform sulphonyl) imines magnesium is the Friedel-Crafts catalyst of methyl-phenoxide and Benzoyl chloride reaction.Its catalytic activity is similar to Zn (NTf 2) 2Find Mg (NTf 2) 2Be the good benzene sulfonyl chloride and the sulfonylation catalyzer of chlorobenzene reaction.
Embodiment 28
The preparation of two (fluoroform sulphonyl) imines aluminium (III)
(0.030g 1.15mmol) joins and places the 25cm that is furnished with magnetic stirring apparatus with aluminium powder 3In the round-bottomed flask two (fluoroform sulphonyl) imines (HN (SO 2CF 3) 2, 0.84g is in distilled water 3.0mmol) (5g) solution.With mixture reflux 0.5 hour.With the mixture cool to room temperature and remove by filter excess of aluminum.Evaporating off water on rotatory evaporator, and by in Minton dryer under 150 ℃ of 1mmHg heat drying two (fluoroform sulphonyl) imines aluminium obtained white powder (0.83g, 96%) in 4 hours.By in Kugelrohr apparatus at 350 ℃ of following vacuum-sublimation purifying two of 1mmHg (fluoroform sulphonyl) imines aluminium (some decomposition take place).Find that unpurified two (fluoroform sulphonyl) imines aluminium is the Friedel-Crafts catalyst of methyl-phenoxide or dimethylbenzene and Benzoyl chloride reaction.Its catalytic activity is similar to Zn (NTf 2) 2
Embodiment 29
The preparation of two (fluoroform sulphonyl) imines manganese (II)
(0.18g 1.6mmol) joins and places the 25cm that is furnished with magnetic stirring apparatus with manganous carbonate (II) 3In the round-bottomed flask two (fluoroform sulphonyl) imines (HN (SO 2CF 3) 2, 0.84g is in distilled water 3.0mmol) (5g) solution.Mixture is stirred 0.5 hour (up to CO 2Effusion stops).Mixture is removed by filter excessive manganous carbonate.Evaporating off water on rotatory evaporator, and by in Minton dryer under 150 ℃ of 1mmHg heat drying two (fluoroform sulphonyl) imines manganese (II) obtained almost powder (0.90g, 97%) in 4 hours for white.By in Kugelrohr apparatus in 280 ℃ of following vacuum distilling/sublimation purification two (fluoroform sulphonyl) imines manganese of 1mmHg (II) (this temperature and pressure seems that the triple point that is in close proximity to this material is fusing point=boiling point).Find that unpurified manganese (II) two (fluoroform sulphonyl) imines is the excellent toluene and the Friedel-Crafts catalyst of Benzoyl chloride reaction.Its catalytic activity is greater than Zn (NTf 2) 2
Embodiment 30
The preparation of two (fluoroform sulphonyl) imines nickel (II)
(0.15g 1.6mmol) joins and places the 25cm that is furnished with magnetic stirring apparatus with nickel hydroxide (II) 3In the round-bottomed flask two (fluoroform sulphonyl) imines (HN (SO 2CF 3) 2, 0.84g is in distilled water 3.0mmol) (5g) solution.Mixture is stirred 1 hour (forming green solution up to the most of dissolving of described oxyhydroxide).Mixture is removed by filter the excessive hydrogen nickel oxide.Evaporating off water on rotatory evaporator, and by in Minton dryer under 150 ℃ of 1mmHg heat drying two (fluoroform sulphonyl) imines nickel (II) obtained very light yellow powder (0.90g, 97%) in 4 hours.By in Kugelrohr apparatus at 280 ℃ of following vacuum distilling/sublimation purification two (fluoroform sulphonyl) imines nickel of 1mmHg (II) (referring to Fig. 6).Find that unpurified two (fluoroform sulphonyl) imines nickel (II) are the excellent toluene and the Friedel-Crafts catalyst of Benzoyl chloride reaction.Its catalytic activity is greater than Zn (NTf 2) 2
Embodiment 31
The preparation of two (fluoroform sulphonyl) imines cobalts (II)
(0.19g 1.6mmol) joins and places the 25cm that is furnished with magnetic stirring apparatus with cobaltous carbonate (II) 3In the round-bottomed flask two (fluoroform sulphonyl) imines (HN (SO 2CF 3) 2, 0.84g is in distilled water 3.0mmol) (5g) solution.Mixture is stirred 1 hour (up to CO 2Effusion stops and forming pink solution).Mixture is removed by filter excessive cobaltous carbonate.Evaporating off water on rotatory evaporator, and by in Minton dryer under 150 ℃ of 1mmHg heat drying two (fluoroform sulphonyl) imines cobalt (II) obtained rose pink powder (0.90g, 97%) in 4 hours.By in Kugelrohr apparatus at 300 ℃ of following vacuum distilling/sublimation purification two (fluoroform sulphonyl) imines cobalts of 1mmHg (II).Find that unpurified two (fluoroform sulphonyl) imines cobalts (II) are the excellent toluene and the Friedel-Crafts catalyst of Benzoyl chloride reaction.Its catalytic activity is greater than Zn (NTf 2) 2Equally, it is one of minority Friedel-Crafts catalyst that is found catalysis chlorobenzene and Benzoyl chloride.
Embodiment 32
The preparation of two (fluoroform sulphonyl) imines copper (II)
(0.20g 1.6mmol) joins and places the 25cm that is furnished with magnetic stirring apparatus with copper carbonate (II) 3In the round-bottomed flask two (fluoroform sulphonyl) imines (HN (SO 2CF 3) 2, 0.84g is in distilled water 3.0mmol) (5g) solution.Mixture is stirred 1 hour (up to CO 2Effusion stops and forming indigo plant/green solution).Mixture is removed by filter excessive copper carbonate (II).Evaporating off water on rotatory evaporator, and by in Minton dryer under 150 ℃ of 1mmHg heat drying two (fluoroform sulphonyl) imines copper (II) obtained utmost point pale green/blue powder (0.89g, 95%) in 4 hours.By in Kugelrohr apparatus at 180 ℃ of following vacuum distilling/sublimation purification two (fluoroform sulphonyl) imines copper of 1mmHg (II) (part takes place in sublimation process decompose, loss is two (fluoroform sulphonyl) the imines copper (II) of half approximately).Find that unpurified two (fluoroform sulphonyl) imines copper (II) are that (catalytic activity is lower than Zn (NTf for the Friedel-Crafts catalyst of toluene, methyl-phenoxide and dimethylbenzene and Benzoyl chloride reaction 2) 2).Equally, find that two (fluoroform sulphonyl) imines copper (II) are good friedel-crafts alkylation catalysts.
Embodiment 33
The preparation of two (fluoroform sulphonyl) imines zinc (II)
(0.13g 2.0mmol) joins and places the 25cm that is furnished with magnetic stirring apparatus with zinc 3In the round-bottomed flask two (fluoroform sulphonyl) imines (HN (SO 2CF 3) 2, 0.84g is in distilled water 3.0mmol) (5g) solution.Mixture is stirred 1 hour (overflow stop and forming colourless solution up to H2).Mixture is removed by filter excess zinc.Evaporating off water on rotatory evaporator, and by in Minton dryer under 150 ℃ of 1mmHg heat drying two (fluoroform sulphonyl) imines zinc (II) obtained white crystals (0.91g, 97%) in 4 hours.A crystal is carried out the analysis of X-radiocrystallography, and its structure is shown in Fig. 5 to 7.By in Kugelrohr apparatus at 1mmHg260 ℃ of following vacuum distilling/sublimation purification two (fluoroform sulphonyl) imines zinc (II).Find that unpurified two (fluoroform sulphonyl) imines zinc (II) are the good Friedel-Crafts catalysts of toluene, methyl-phenoxide and dimethylbenzene and Benzoyl chloride reaction and phenylformic acid and dimethylbenzene reaction.Equally, find that it is one of the minority friedel-crafts acylation reaction catalyst of the acylation reaction of catalysis chlorobenzene and Benzoyl chloride.
Embodiment 34
Two (fluoroform sulphonyl) imines indiums (III)
Be dissolved in 5.0g indium hydroxide (III) in the 50ml water and to wherein adding 27.0gNHTf 2, at room temperature stirred 24 hours.Reaction mixture is filtered and filtrate is concentrated on rotatory evaporator, vacuum (1mmHg), 120 ℃ of dryings 3 days.Find that unpurified two (fluoroform sulphonyl) imines indiums (III) are the good Friedel-Crafts catalysts of toluene, methyl-phenoxide and dimethylbenzene and Benzoyl chloride or benzoyl oxide reaction.
Embodiment 35
Gallium (III) Triflamide
Be suspended in 2.5g oxygen in the 50ml water and add 24.0g three gallium fluorides (III) methylsulfonyl imines, 100 ℃ of heating two days.With reaction mixture filtration and filtrate is concentrated and following dry 3 days in 120 ℃ in vacuum (1mmHg) on rotatory evaporator.Find that unpurified two (fluoroform sulphonyl) imines galliums (III) are the good Friedel-Crafts catalysts of toluene, methyl-phenoxide and dimethylbenzene and Benzoyl chloride or benzoyl oxide reaction.
Embodiment 36
Two (fluoroform sulphonyl) imines calcium
1.0g lime carbonate (II) is suspended in the 50mL water, to wherein adding the HNTf that has just prepared 2(5.6g) also at room temperature stirred 24 hours.With reaction mixture filtration and filtrate is concentrated and following dry 4 hours in 150 ℃ in vacuum (1mmHg) on rotatory evaporator.Find that unpurified two (fluoroform sulphonyl) imines calcium shows the Friedel-Crafts reaction catalytic activity of going on business.
Embodiment 37
Two (fluoroform sulphonyl) imines strontiums (II)
1.0g Strontium carbonate powder (II) is suspended in the 50mL water, to wherein adding the HNTf that has just prepared 2(3.8g) also at room temperature stirred 24 hours.With reaction mixture filtration and filtrate is concentrated and following dry 4 hours in 150 ℃ in vacuum (1mmHg) on rotatory evaporator.Find that unpurified two (fluoroform sulphonyl) imines strontiums (II) show the Friedel-Crafts reaction catalytic activity of going on business, but higher slightly than calcium analogue activity.
Embodiment 38
Two (fluoroform sulphonyl) imines barium
1.0g barium carbonate (II) is suspended in the 50mL water, to wherein adding the HNTf that has just prepared 2(2.8g) also at room temperature stirred 24 hours.With reaction mixture filtration and filtrate is concentrated and following dry 4 hours in 150 ℃ in vacuum (1mmHg) on rotatory evaporator.Find that unpurified two (fluoroform sulphonyl) imines barium (II) demonstrate some Friedel-Crafts reaction catalytic activitys, active higher than calcium and strontium analogue.
Embodiment 39
Two (fluoroform sulphonyl) imines tin (II) methods 1
Be suspended in tin metal (5.0g, 99.9% purity) piece in the water (50mL) and add two (fluoroform sulphonyl) imines (HNTf 2) (10g).With this mixture reflux 72 hours.The mixture that obtains is cooled off, filters and concentrates and the formation colourless solution on rotatory evaporator, crystallization when it is placed.The canescence crystal is added heat abstraction residuary water and two (fluoroform sulphonyl) imines at 150 ℃ of lmmHg.Find that unpurified two (fluoroform sulphonyl) imines tin (II) demonstrate catalytic activity in Friedel-Crafts reaction (as 1%Sn (NTf 2) 2+ toluene+Benzoyl chloride obtains 99% yield after refluxing 48 hours).Its activity is similar to two (fluoroform sulphonyl) imines zinc.
Embodiment 40
Two (fluoroform sulphonyl) imines tin (II) methods 2
With stannic oxide (II) (1.0g) powder suspension in water (50mL) and add two (fluoroform sulphonyl) imines (HNTf 2) (5.0g).This mixture of reflux 48 hours.With the cooling of the slurry that obtains, filter and on rotatory evaporator, concentrate and obtain colourless solution, it forms pale precipitation when placing.The heating pale precipitation is to remove residuary water and two (fluoroform sulphonyl) imines under 150 ℃ of 1mmHg.Find that unpurified two (fluoroform sulphonyl) imines tin (II) demonstrate catalytic activity in Friedel-Crafts reaction (as 1%Sn (NTf 2) 2+ toluene+Benzoyl chloride obtains 99% yield after refluxing 6 hours).
Embodiment 41
Two (fluoroform sulphonyl) imines lead (II)
13.0g lead carbonate (II) is put in the 50mL water, to wherein adding the HNTf that 28.0g has just prepared 2And at room temperature stirred 24 hours.With reaction mixture filtration and filtrate is concentrated and following dry 3 days in 120 ℃ in vacuum (1mmHg) on rotatory evaporator.Find that unpurified two (fluoroform sulphonyl) imines lead (II) demonstrate good Friedel-Crafts reaction catalytic activity (as 1%Pb (NTf 2) 2+ toluene+Benzoyl chloride obtains 99% yield after refluxing 48 hours).Its catalytic activity is better than two (fluoroform sulphonyl) imines zinc (II).
Embodiment 42
Two (fluoroform sulphonyl) imines chromium (III)
Be suspended in chromium metal (1.0g, 99.95% purity) sheet in the water (20mL) and add two (fluoroform sulphonyl) imines (HNTf 2) (5g).With mixture reflux 144 hours.With the cooling of the mixture that obtains, filter and on rotatory evaporator, concentrate and obtain green solid.The heat solid thing is to remove residuary water and two (fluoroform sulphonyl) imines under 150 ℃ of 1mmHg.Described solids is considered to comprise the HNTf that produces from drying process 2Two (fluoroform sulphonyl) imines chromic oxide class substance C rO (NTf 2).Find that unpurified two (fluoroform sulphonyl) imines chromium (III) demonstrate the catalytic activity of Friedel-Crafts reaction, and its activity is similar to Zn (NTf 2) 2
Embodiment 43
Two (fluoroform sulphonyl) imines tungsten
Be suspended in tungsten metal (1.0g, 99% purity) bits in the water (20mL) and add two (fluoroform sulphonyl) imines (HNTf 2) (5g).With mixture reflux 144 hours.With the cooling of the slurry that obtains, filter and on rotatory evaporator, concentrate and obtain colourless solution, its crystallization when placing.Under 150 ℃ of 1mmHg, add thermal crystalline to remove residuary water and two (fluoroform sulphonyl) imines.Precision architecture the unknown of described catalyzer, but find its be in Benzoyl chloride and reaction of toluene, test best in separative metal two (fluoroform sulphonyl) imine catalyst.
Embodiment 44
Two (fluoroform sulphonyl) imines iron (II)
Be suspended in ferrous metal (5.0g, 99.95% purity) piece in the water (50mL) and add two (fluoroform sulphonyl) imines (HNTf 2) (10g).With mixture reflux 72 hours.With the cooling of the slurry that obtains, filter and on rotatory evaporator, concentrate and obtain yellow solution, its crystallization when placing.The faint yellow crystallization of heating is to remove residuary water and two (fluoroform sulphonyl) imines under 150 ℃ of 1mmHg.
Embodiment 45
Two (fluoroform sulphonyl) imines iron (III)
This compound can (be thought Fe (NTf by the creamy white crystal 2) 2(OH) (OH 2)) form or brown solid (be considered to FeO (NTf 2)) isolated in form.Add sodium hydroxide solution (1M) up to forming the brown precipitate thing to iron nitrate (III) aqueous solution (10g).Collecting hydronium(ion) oxidation iron (III) by vacuum filtration precipitates and washes with water.Be suspended in throw out (about 5g) in the distilled water and add two excessive (fluoroform sulphonyl) imines (20g).Throw out slowly dissolves and forms transparent light brown solution.Solution is filtered and on rotatory evaporator, concentrate and transfer in the Kugelrohr apparatus device.Unreacted two (fluoroform sulphonyl) imines distills under 100 ℃ of 1mmHg, stays creamy white hydration two (fluoroform sulphonyl) imines iron (III) crystalline solid.Under 170 ℃ of 1mmHg, heated 4 hours again, cause two (fluoroform sulphonyl) imines to be overflowed, and form brown solid (FeO (NTf 2)).Find that these two kinds of solids all are toluene and the excellent Friedel-Crafts catalyst (concentration of 1% (mole)) of Benzoyl chloride reaction.
Embodiment 46 is based on the preparation on the spot of metal two (fluoroform sulphonyl) group with imine moiety of palladium (II) and two (fluoroform sulphonyl) imines ion
(II) (0.035g) joins at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger with Palladous chloride 3Two-fluoroform sulfimide 1-butyl-3-Methylimidazole _ ([bmim] [NTf in the round-bottomed flask 2]) (2.0g) in.Under agitation its mild heat is formed the yellow/orange clear solution up to Palladous chloride (II) dissolving.Then this solution is used as the friedel-crafts acylation catalyst.
(2.81g, 30mmol) (2.84g tests Palladous chloride (II)/[bmim] [NTf in reaction 20mmol) with Benzoyl chloride at toluene 2] catalytic activity of composition.Detect with mixture heating up backflow 24 hours and by gas chromatographic analysis.It forms methyldiphenyl ketone (75% yield, 4.5: 1 contraposition and ortho position ratio).
Embodiment 47 is based on the preparation on the spot of metal two (fluoroform sulphonyl) group with imine moiety of tungsten (IV) and two (fluoroform sulphonyl) imines ion
(0.079g) joins at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger with tungsten chloride 3Two-fluoroform sulfimide 1-butyl-3-Methylimidazole _ ([bmim] [NTf in the round-bottomed flask 2]) (2.0g) in.Under agitation its mild heat is formed clear solution up to tungsten chloride (VI) dissolving.Then this solution is used as the friedel-crafts acylation catalyst.
(2.81g, 30mmol) (2.84g tests tungsten chloride (VI)/[bmim] [NTf in reaction 20mmol) with Benzoyl chloride at toluene 2] catalytic activity of composition.Detect with mixture heating up backflow 24 hours and by gas chromatographic analysis.It forms methyldiphenyl ketone (99% yield, 4.1: 1 contraposition and ortho position ratio).
Embodiment 48 is based on the preparation on the spot of metal two (fluoroform sulphonyl) group with imine moiety of tin (IV) and two (fluoroform sulphonyl) imines ion
(IV) (0.052g) joins at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger with tin chloride 3Two-fluoroform sulfimide 1-butyl-3-Methylimidazole _ ([bmim] [NTf in the round-bottomed flask 2]) (2.0g) in.Stirring forms clear solution up to tin chloride (IV) dissolving.Then this solution is used as the friedel-crafts acylation catalyst.
(2.81g, 30mmol) (2.84g tests tin chloride (IV)/[bmim] [NTf in reaction 20mmol) with Benzoyl chloride at toluene 2] catalytic activity of composition.Detect with mixture heating up backflow 24 hours and by gas chromatographic analysis.It forms methyldiphenyl ketone (99% yield, 4.2: 1 contraposition and ortho position ratio).
Embodiment 49: based on the preparation on the spot of metal two (fluoroform sulphonyl) group with imine moiety of titanium (IV) and two (fluoroform sulphonyl) imines ion
(IV) (0.038g) joins at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger with titanium chloride 3Two-fluoroform sulfimide 1-butyl-3-Methylimidazole _ ([bmim] [NTf in the round-bottomed flask 2) (2.0g) in.Stirring forms clear solution up to titanium chloride (IV) dissolving.Then this solution is used as the friedel-crafts acylation catalyst.
(2.81g, 30mmol) (2.84g tests titanium chloride (IV)/[bmim] [NTf in reaction 20mmol) with Benzoyl chloride at toluene 2] catalytic activity of composition.Detect with mixture heating up backflow 24 hours and by gas chromatographic analysis.It forms methyldiphenyl ketone (99% yield, 4.5: 1 contraposition and ortho position ratio).
Embodiment 50: based on the preparation on the spot of metal two (fluoroform sulphonyl) group with imine moiety of hafnium (IV) and two (fluoroform sulphonyl) imines ion
(IV) (0.064g) joins at the 25cm that is furnished with magnetic stirring apparatus and reflux exchanger with hafnium chloride 3Two-fluoroform sulfimide 1-butyl-3-Methylimidazole _ ([bmim] [NTf in the round-bottomed flask 2]) (2.0g) in.Stirring forms clear solution up to hafnium chloride (IV) dissolving.Then this solution is used as the friedel-crafts acylation catalyst.
(2.81g, 30mmol) (2.84g tests hafnium chloride (IV)/[bmim] [NTf in reaction 20mmol) with Benzoyl chloride at toluene 2] catalytic activity of composition.Detect with mixture heating up backflow 24 hours and by gas chromatographic analysis.It forms methyldiphenyl ketone (99% yield, 4.42: 1 contraposition and ortho position ratio).

Claims (10)

1. one kind is used to carry out electrophilic substitution or isomery, the polymerization of aromatic ring or be rearranged into compound or the method for molecule, and this method is by the metal two of following formula (fluoroform sulphonyl) group with imine moiety catalysis and solvation under condition of no solvent or in the presence of ionic liquid
[M x] n+[(N(SO 2CF 3) 2) (nx-yz)] (nx-yz)-[L y] z-
M is the metal that is selected from periodic table of elements 5-10 family, 12 families and 14-16 family and Cu, Au, Ca, Sr, Ba, Ra, Y, La, Ac, Hf, Rf, Pb, Ga, In, Tl, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and actinide elements in the formula;
L is negativity or neutral ligand;
N is 2,3,4,5,6,7 or 8;
X is more than or equal to 1;
Y is 0,1,2,3,4,5,6,7 or 8; And
Z is 0,1,2,3 or 4.
2. the process of claim 1 wherein that M is selected from the metal of the periodic table of elements 7,8,9,10,12 and 14 families.
3. the process of claim 1 wherein that M is selected from Mn, Fe, Co, Ni, Ga, In, Zn and Pb.
4. the method for claim 3, wherein M is selected from Mn (II), Fe (III), Co (II), Ni (II), In (II), Pb (II), In (III) and Ga (III).
5. each method of claim 1-4, the concentration of wherein said metal two (fluoroform sulphonyl) imines is the 0.1-20% mole.
6. the method for claim 5, wherein said concentration is the 0.5-5% mole.
7. each method of claim 1-4, wherein said reaction is the reaction between aromatic substance and alkylating agent, acylating agent or the sulphonating agent.
8. each method of claim 1-4, wherein said reaction is the Fries rearrangement of 4-methylphenoxy benzoic ether and hydrogen.
9. each method of claim 1-4, wherein said catalyzer uses under condition of no solvent or in the presence of ionic liquid, and separates from reaction mixture subsequently.
10. the method for claim 9, wherein said catalyzer is recycled subsequently.
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